EP3022255A1 - Composites polymère-nanofibrille - Google Patents

Composites polymère-nanofibrille

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Publication number
EP3022255A1
EP3022255A1 EP14826568.9A EP14826568A EP3022255A1 EP 3022255 A1 EP3022255 A1 EP 3022255A1 EP 14826568 A EP14826568 A EP 14826568A EP 3022255 A1 EP3022255 A1 EP 3022255A1
Authority
EP
European Patent Office
Prior art keywords
cnfs
composite
mapp
cellulose
nanofibril
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14826568.9A
Other languages
German (de)
English (en)
Other versions
EP3022255B1 (fr
EP3022255A4 (fr
Inventor
Douglas J. Gardner
Yousoo Han
Yucheng Peng
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University of Maine System
Original Assignee
MAINE SYS BOARD TRUSTEES, University of
University of Maine System
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/14—Copolymers of polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2073/00—Use of other polymers having oxygen as the only hetero atom in the main chain, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2201/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the present invention provides, among other things, composite materials comprising nanofibrils, a maleic-anhydride (MA) copolymer and a matrix polymer, and methods of making such compositions.
  • the provided methods and composite materials exhibit unexpectedly superior properties including improved impact resistance, tensile modulus of elasticity, tensile strength, and flexural modulus of elasticity, as compared to previously known composites.
  • the present invention provides methods including the steps of providing cellulose nanofibrils, associating the cellulose nanofibrils with a maleic-anhydride (MA) copolymer to form a nanofibril-MA copolymer blend, preparing the nanofibril-MA copolymer blend for addition to a matrix polymer, and forming a composite by associating the nanofibril-MA copolymer blend with the matrix polymer, wherein the amount of cellulose nano fibrils in the composite is between 3% and 50% by weight of the composite.
  • the preparing step comprises drying the nanofibril-MA copolymer blend. In some embodiments, drying is spray drying.
  • preparing a nanofibril-MA copolymer blend for addition to a matrix polymer may take any application-appropriate form.
  • the preparing step includes drying the nanofibril-MA-copolymer blend, cooling the dried nanofibril-MA-copolymer blend, and granulating the dried nanofibril-MA-copolymer blend to form a nanofibril-MA-copolymer masterbatch.
  • the conditions in which the associating step occurs may vary in accordance with the desired form and properties of the desired composite material.
  • the associating step occurs at a temperature between 130°C and 220°C, inclusive.
  • the associating step comprises mixing of the cellulose nanofibrils and maleic-anhydride (MA) copolymer for between 1 minute and 60 minutes, inclusive.
  • Provided methods and compositions may include the use of substantially dry components (e.g., nanofibrils, MA-copolymers, and matrix polymers) and/or the use of one or more components that are not dry, such as components in solution.
  • substantially dry components e.g., nanofibrils, MA-copolymers, and matrix polymers
  • cellulose nanofibrils are in solution at the time of initiating the associating step.
  • maleic-anhydride copolymer comprises the dispersed phase of an emulsion at the time of initiating the associating step.
  • cellulose nanofibrils are substantially dry at the time of initiating the associating step.
  • substantially dry means the nanofibrils (or other component) contain less than 1% moisture content based on the oven dry weight of the nanofibrils (or other component).
  • various embodiments provide composites with improved properties.
  • provided composites are characterized as having an impact resistance that is higher than that of a composite consisting of the matrix polymer and cellulose nanofibrils.
  • the impact resistance of the composite is at least 20% (e.g., 25%, 30%, 35%), 40%), 45%, or 50%>) greater than that of a composite consisting of the matrix polymer and cellulose nanofibrils.
  • provided composites are characterized as having a tensile modulus of elasticity at least 35% higher than that of a composite consisting of the matrix polymer and cellulose nanofibrils. In some embodiments, provided composites are characterized as having a tensile strength at least 10% higher than that of a composite consisting of the matrix polymer and cellulose nanofibrils.
  • a maleic-anhydride polymer is selected from a maleic-anhydride olefin polymer and a maleic-anhydride polystyrene.
  • a maleic-anhydride olefin copolymer is maleic-anhydride polypropylene or maleic-anhydride polyethylene.
  • a composite is formed via any of a variety of processes.
  • a composite is formed via an extrusion, compression molding, injection molding, and/or fused layer modeling process (e.g., 3D printing).
  • the present invention also provides composite materials with improved properties.
  • the composite material is produced according to one of the methods described herein.
  • FIG. 1 shows a flow diagram depicting certain exemplary embodiments.
  • FIG. 2 shows a graph of exemplary particle size distributions (PSD) of cellulose nanofibrils (CNFs) in suspension or dry form.
  • CNF represents the PSD of spray-dried CNF.
  • MAPP_CNF represents the PSD of spray-dried CNFs treated by MAPP emulsion.
  • CNF_1 represents the original PSD of CNFs in suspension.
  • CNF 2 represents the PSD of the mixture of CNFs and MAPP emulsion before ultrasonic treatment.
  • CNF 3 represents the PSD of the mixture of CNFs and MAPP emulsion after ultrasonic treatment.
  • MAPP indicates the PSD of solid content in MAPP emulsion.
  • FIG. 3A-B shows exemplary SEM micrograms of spray-dried CNFs: panel (A) x
  • FIG. 4 shows an exemplary graph of the modulus of elasticity and tensile strength of certain embodiments as tested according to ASTM D 638-10.
  • FIG. 5A-F shows exemplary SEM micrograms of composites comprising PP and/or PP+MAPP.
  • Panel A fractured sample surface
  • panel B fractured sample cross-section
  • panels C, D, E, and F show exemplary regions 1, 2, 3, and 4 in sample cross-section.
  • FIG. 6A-F shows exemplary SEM micrograms of CNF-reinforced PP.
  • PP+MAPP CNF panels B and C: PP+CNF, panel D: PP+MAPP CNF, panels E and F:
  • FIG. 7 shows an exemplary graph of the modulus of elasticity and tensile strength of certain embodiments as tested according to ASTM D 790-10.
  • FIG. 8 shows a graph of impact resistance of certain embodiments.
  • FIG. 9A-F show exemplary fracture cross-sections of certain embodiments after impact tests at 120X, 200X, or 2,000X magnification.
  • Panels A and B PP
  • panels C and D PP+CNF
  • panels E and F PP+MAPP CNF.
  • FIG. 10A-F show exemplary fracture cross-sections of certain embodiments after impact tests at 120X, 200X, 5,000X, or 10,000X magnification.
  • Panels A, C, and E PP+MAPP
  • panels B, D, and F PP+MAPP+CNF.
  • FIG. 11A-C show graphs of the mechanical properties of certain embodiments comprising cellulose nanoparticle (CNP)-reinforced polypropylene (6% loading of CNP).
  • Panel A shows the tensile modulus and tensile strength of certain embodiments
  • panel B shows the flexural modulus and strength of certain embodiments
  • panel C shows the impact strength of certain embodiments.
  • FIG. 12 shows a graph of the increase in certain tensile properties exhibited by certain embodiments.
  • FIG. 13 shows a graph of the increase in certain flexural properties exhibited by certain embodiments.
  • FIG. 14 shows a graph of the increase in impact strength exhibited by certain embodiments.
  • the term “a” may be understood to mean “at least one”;
  • the term “or” may be understood to mean “and/or”;
  • the terms “comprising” and “including” may be understood to encompass itemized components or steps whether presented by themselves or together with one or more additional components or steps; and
  • the terms “about” and “approximately” may be understood to permit standard variation as would be understood by those of ordinary skill in the art; and (v) where ranges are provided, endpoints are included.
  • the term “approximately” and “about” is intended to encompass normal statistical variation as would be understood by those of ordinary skill in the art.
  • the term “approximately” or “about” refers to a range of values that fall within 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%), 7%), 6%), 5%, 4%, 3%, 2%, 1%, or less in either direction (greater than or less than) of the stated reference value unless otherwise stated or otherwise evident from the context (except where such number would exceed 100% of a possible value).
  • the term “substantially” refers to the qualitative condition of exhibiting total or near-total extent or degree of a characteristic or property of interest.
  • One of ordinary skill in the art will understand that chemical phenomena rarely, if ever, go to completion and/or proceed to completeness or achieve or avoid an absolute result.
  • the term “substantially” is therefore used herein to capture the potential lack of completeness inherent in many chemical phenomena.
  • the present invention provides, among other things, composite materials with enhanced properties, and methods of making those materials.
  • provided composite materials comprise nanofibrils, a maleic-anhydride (MA) copolymer and a matrix polymer.
  • MA maleic-anhydride
  • provided methods and composite materials exhibit unexpectedly superior properties including improved impact resistance, tensile modulus of elasticity, tensile strength, and flexural modulus of elasticity, as compared to previously known composites.
  • the present invention provides methods including the steps of providing cellulose nanofibrils, associating the cellulose nanofibrils with a maleic-anhydride (MA) copolymer to form a nanofibril-MA copolymer blend, preparing the nanofibril-MA copolymer blend for addition to a matrix polymer, and forming a composite by associating the nanofibril-MA copolymer blend with the matrix polymer, wherein the amount of cellulose nanofibrils in the composite is between 3% and 50% by weight of the composite.
  • the preparing step comprises drying the nanofibril-MA copolymer blend. In some embodiments, the drying is spray drying.
  • thermoplastic resins Compared to the conventional reinforcements such as glass fibers or inorganic fillers, cellulosic materials offer a series of advantages: lower density (1.5 g/cm 3 ), better recyclability and disposal, lower price, reduced abrasion to processing machinery, and carbon dioxide neutrality.
  • Cellulose is a high molecular weight linear syndiotactic homopolymer composed of D-anhydroglucopyranose units (AGU) which are linked together by P-(l ⁇ 4)-glycosidic bonds.
  • AGU D-anhydroglucopyranose units
  • P-(l ⁇ 4)-glycosidic bonds The natural affinity for self-adhesion of cellulose chains allows for formation of CNFs with crystalline and amorphous domains. These CNFs may form the basic aggregation units to form microfibrils or cellulose fibers such as pulp fibers.
  • the elastic modulus of cellulose increases from about 10 GPa to 70 GPa or, in some cases, even higher (145 GPa).
  • the strength-to-weight ratio of cellulose nanocrystals is reported to be eight times higher (see Ferguson W, Why wood pulp is world's new wonder material, 2012, New Scientist, 2878: 24; see also Cranston et al,
  • cellulose nanofibrils also referred to as nanocellulose
  • CNF Cellulose nanofibrils
  • NFC aiiofibriliated cellulose
  • CNC nanocrystals
  • a cellulose nanofibril may be a fiber or particle having any shape wherein at least one dimension (e.g., diameter, width, thickness, and/or length) of about 100 nanometers or less.
  • cellulose nanofibrils may have a diameter between 5 and 20 (e.g., about 5 to 15, about 5 to 10) nanometers, inclusive.
  • cellulose nanofibrils may have a length between about 10 and 5,000 ⁇ e.g., about 10 to 4,000, about 10 to 3,000, about 10 to 2,000, about 10 to 1,000, or about 10 to 500) nanometers, inclusive.
  • cellulose nanofibrils may be pretreated before association with an MA-copolymer.
  • pretreatment may be an enzymatic pretreatment, chemical pretreatment, and/or a mechanical pretreatment.
  • enzymatic pretreatment is or comprises treatment with a cellulase (e.g., an A-, B-, C-, and/or D-type cellulase).
  • chemical pretreatment is or comprises 2, 2, 6, 6-tetramethyl-l- piperidinyloxy (TEMPO)-mediated oxidation.
  • pretreatment may be or comprise the introduction of charged group to the nanofibrils (e.g., through carboxymethylation).
  • pretreatment may be or comprise acetylation of cellulose nanofibrils.
  • cellulose nanofibrils may be isolated from any cellulosic material.
  • cellulose nanofibrils are isolated from wood- based material, such as, for example, woodpulp (e.g., bleached Kraft pulp and/or bleached sulfite pulp).
  • cellulosic nanofibrils may be or comprise wood fibers, paper fibers, pulp fibers, rice-husk flour, flax, jute, sisal, microcrystalline cellulose (MCC),
  • nanofibrillated cellulose NFC
  • CNCs cellulose nanocrystals
  • nanofibrillated cellulose and cellulose nanocrystals are generally considered the elementary fibrils of cellulose materials, e.g., cellulose nanofibrils (CNFs).
  • Maleic anhydride (MA) is an organic compound with a chemical formula of
  • a MA copolymer is a MA-olefm copolymer.
  • suitable MA-olefm copolymers are those that provide desirable properties to a particular provided composite material.
  • olefin copolymers that are suitable for use according to various embodiments include, but are not limited to ethylene; alpha olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene and 1-dodecene; 2-butene; 2-pentene; 2-hexene; 2-octene; and combinations thereof.
  • polypropylene has been widely used because of its low price, light weight, good weathering ability, design flexibility, recyclability, and its attractive combination of good processability, mechanical properties, and chemical resistance.
  • PP polypropylene
  • MFI melt flow indices
  • thermoplastic and even engineering thermoplastics such as polycarbonate (PC) and acrylonitrile butadiene styrene (ABS).
  • PC polycarbonate
  • ABS acrylonitrile butadiene styrene
  • Reinforced PP composites can be produced with many different types of fillers using various processing techniques including injection molding, compression molding, blow molding, extrusion, and thermo forming. Recent developments in filled PP composites showed that high performance materials can be obtained by reinforcing PP using
  • an MA-copolymer is MA-polypropylene (see the Examples below for some such exemplary embodiments).
  • a MA copolymer is a MA-polystyrene.
  • Any suitable styrenic monomer can be used as one or more of the primary monomers according to various embodiments.
  • Suitable styrenic monomers include those that provide the desirable properties to a particular provided composite materials.
  • Non-limiting examples of suitable styrenic monomers include, but are not limited to styrene, p-methyl styrene, a-methyl styrene, tertiary butyl styrene, dimethyl styrene, nuclear brominated or chlorinated derivatives thereof and combinations thereof.
  • associating cellulose nanofibrils with MA- copolymers may occur in any of a variety of ways.
  • the association occurs under substantially dry conditions.
  • both the cellulose nanofibrils and MA-copolymer are substantially dry (e.g., contain less than 1% moisture content based on the oven dry weight of the material).
  • the present invention provides methods of associating cellulose nanofibrils and MA-copolymers under non-dry conditions.
  • at least one of cellulose nanofibrils and MA-copolymers are in solution at the time the associating step is initiated.
  • at least one of cellulose nanofibrils and MA-copolymers comprise a portion of am emulsion at the time the associating step is initiated (e.g., an MA- copolymer is or comprises the dispersed phase of an emulsion).
  • the associating step may occur at any of a variety of temperatures.
  • the associating step may occur at a temperature between about 80°C and 220°C (e.g., about 80°C and 200°C, about 80°C to 150°C, about 80°C to 100°C, about 100°C to 200°C), inclusive.
  • the associating step occurs at a temperature at or above 80°C (e.g., 90°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C).
  • the associating step occurs at a temperature at or below 220°C (e.g., 200°C, 180°C, 160°C, 140°C, 120°C, 100°C, 90°C, 80°C).
  • the temperature remains constant during the associating step.
  • the temperature increases during the associating step.
  • the temperature decreases during the associating step.
  • the temperature fluctuates during the associating step.
  • the length of time during which the associating step occurs may vary.
  • the associating step is between about 1 minute and 60 minutes in duration (e.g. , about 5 to 60 minutes, about 5 to 50 minutes, about 5 to 40 minutes, about 5 to 30 minutes, about 5 to 20 minutes, about 5 to 10 minutes).
  • the associating step occurs for at least one minute (e.g. at least 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 minutes).
  • the associating step occurs for less than 60 minutes (e.g., less than 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2 minutes).
  • associating refers to simple mixing of cellulose nanofibrils and MA-copolymers in a vessel or container. In some embodiments, associating refers to simple addition of both cellulose nanofibrils and MA-copolymer(s) to a vessel of container (e.g., associating occurs via simple diffusion or another passive process). In some embodiments associating involves active mixing. In some embodiments active mixing may be or comprise stirring, sonication, or other agitation.
  • the associating step comprises combining cellulose nanofibrils in suspension with MA-copolymers (e.g., MAPP) in an emulsion during a spray- drying process.
  • the associating step comprises mixing dried cellulose nanofibrils with MA-copolymer pellets and a matrix polymer during an extrusion process.
  • preparing a nanofibril-MA copolymer blend for addition to a matrix polymer includes drying the nanofibril MA-copolymer blend.
  • Exemplary, non-limiting methods of drying cellulose nanofibrils include those described in U.S. Patent 8,372,320, issued on February 12, 2013, the disclosure of which is hereby incorporated by reference in its entirety.
  • preparing may be or comprise one or more of the following steps: drying the nanofibril MA-copolymer blend, cooling the dried nanofibril MA- copolymer blend, and granulating the dried nanofibril MA-copolymer blend to form a nanofibril MA-copolymer masterbatch.
  • drying may be or comprise spray drying.
  • spray drying is defined as a processing method to convert a suspension, solution, or emulsion into a solid powder in one single process step.
  • Spray drying involves evaporation of moisture from an atomized feed or spray of the suspension by mixing the spray and a drying medium.
  • the drying medium is typically air or nitrogen.
  • cooling may be or comprise removing a nanofibril MA- copolymer blend from a heat source (e.g., air cooling).
  • cooling may be or comprise active cooling (e.g., refrigeration and/or freezing).
  • granulating may be or comprise grinding, ablating, and/or another form of converting a mass of material into smaller component pieces of the material. In some embodiments, granulating may be or comprise pelletizing. As used herein, the term
  • Pellets refers to compressing or molding a material into the shape of a pellet. Pellets may be of any application- and/or material-appropriate shape and/or size.
  • the result of the associating and/or preparing step may be or comprise a masterbatch of dry or substantially dry nanofibril MA-copolymer blend (e.g., as dry or substantially dry pellets, granules or other industrially useful form).
  • the specific method used to form a particular provided composite material may vary according to the desired mechanical, flexural, or other properties and may occur via any appropriate methods.
  • two methods are generally used to produce polymer nanocomposites based on different polymer matrices.
  • the first, solution casting, is the method typically used in solvent-based systems including aqueous dispersed polymers, i.e. latexes and organic solvent-based systems.
  • compounding CNFs in a dry form with polymer melts through the extrusion process is desirable. Drying CNFs while maintaining their nano-scale dimensions has been studied in detail and dry forms of CNFs can be produced by, for example, the spray-drying method developed by Dr. Gardner's group at the University of Maine (see Peng et al., Drying cellulose nanofibrils: in search of a suitable method, 2012, Cellulose, 19(1): 91-102; see also Peng et al., Spray-drying cellulose nanofibrils: effect of drying process parameters on particle morphology and size distribution, 2012, Wood and Fiber Sci, 44(4): 1-14).
  • CNF -reinforced PP nanocomposites is associated with surface properties of the dried CNFs.
  • the incompatibility between the hydrophilic cellulose fibers and the hydrophobic polypropylene was observed to seriously degrade the mechanical properties of the composites and is thought to be due, at least in part, to the high density of hydroxyl groups on the surface of the CNFs.
  • the hydrogen bonds between the hydroxyl groups allow for undesired adhesion between cellulose fibers.
  • cellulose fibrils can interact and agglomerate easily when in close proximity to each other.
  • the cellulose fiber can be subjected to specific surface modifications to: 1) decrease the agglomeration, 2) provide an efficient hydrophobic barrier, and 3) minimize their interfacial energy with the non-polar polymer matrix and thus generate optimum adhesion. Further improvement in this interfacial strength, which is a basic requirement for the mechanical performance of some embodiments, is attained by chain entanglement between the matrix macromolecules and long chains appended to the fiber surface or, in some embodiments, by the establishment of a continuity of covalent bonds at the interface between the two components of the composite.
  • cellulose chemical moieties exploited for this purpose are its hydroxyl functional groups, which have been the source of well-known reactions used to prepare a wide array of cellulose derivatives, including esters, ethers, etc. According to various embodiments, such modifications are limited to the superficial - OH groups to preserve the integrity of the fibers and thus their mechanical strength.
  • a provided composite is
  • compositions are characterized as having an impact resistance that is higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided compositions are characterized as having an impact resistance at least 5% (e.g, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%) higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • a provided composite is characterized as having a tensile modulus of elasticity that is higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided compositions are
  • provided composite materials may exhibit increased tensile modulus eleasticity as compared to a composite consisting of only the matrix polymer and cellulose nanofibrils while maintaining a level of impact resistance at or above the impact resistance exhibited by the composite consisting of only the matrix polymer and cellulose nanofibrils.
  • a provided composite is characterized as having a tensile strength that is higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided compositions are characterized as having a tensile strength at least 5% (e.g., 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%) higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided composite materials may exhibit increased tensile strength as compared to a composite consisting of only the matrix polymer and cellulose nanofibrils while maintaining a level of impact resistance at or above the impact resistance exhibited by the composite consisting of only the matrix polymer and cellulose nanofibrils.
  • a provided composite is characterized as having a flexural modulus of elasticity that is higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided compositions are
  • provided composite materials may exhibit increased flexural modulus eleasticity as compared to a composite consisting of only the matrix polymer and cellulose nanofibrils while maintaining a level of impact resistance at or above the impact resistance exhibited by the composite consisting of only the matrix polymer and cellulose nanofibrils.
  • a provided composite is characterized as having a flexural strength that is higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided compositions are characterized as having a flexural strength at least 5% (e.g., 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%) higher than that of a composite consisting of only the matrix polymer and cellulose nanofibrils.
  • provided composite materials may exhibit increased flexural strength as compared to a composite consisting of only the matrix polymer and cellulose nanofibrils while maintaining a level of impact resistance at or above the impact resistance exhibited by the composite consisting of only the matrix polymer and cellulose nanofibrils.
  • compositions are able to achieve reinforced polypropylene nanocomposite materials with surprisingly advantageous properties.
  • the polypropylene (PP) used as the thermoplastic matrix polymer in this Example was supplied by INEOS Olefins & Polymers USA (League City, Texas) and is marketed under the commercial name of H05A-00 polypropylene homopolymer.
  • the density of the PP matrix was 0.89 - 0.93 g/cm 3 .
  • the melt flow index for this material was 4.70 g/10 min under the temperature of 230 °C at the load of 2.16 kg.
  • the CNF suspension was stored in a plastic container at room temperature before drying.
  • FGLASSTM X35 and the maleic anhydride modified homopolymer polypropylene (MAPP) pellets (Polybond 3200) were provided by Michelman, Inc. (Cincinnati, Ohio) and Chemtura Corporation (Lawrenceville, Georgia).
  • MAPP maleic anhydride modified homopolymer polypropylene
  • the main non-volatile was maleated polypropylene with the solid content of 34 - 36 wt. %.
  • the specific gravity for the emulsion was 0.96 - 0.98 g/cm 3 .
  • the Brookfield viscosity of the emulsion with spindle number 2 rotating at 60 RPM was about 200 cps.
  • the maleic anhydride level in Polybond 3200 pellets was about 1.0 wt. %.
  • the melting point and density of Polybond 3200 was 157 °C and 0.91 g/cm 3 .
  • the melt flow at 190 °C with the load of 2.16 kg was 115 g/10 minute.
  • a thermal compounding process was used to manufacture the CNFs reinforced PP nanocomposites.
  • the composite formulations are shown in Table 1.
  • CNFs in dry form were obtained through a spray-drying process first.
  • the concept of "masterbatching” was employed to disperse the CNFs into the polymer matrix (PP or MAPP).
  • Masterbatching is typically used in the plastic compounding field for coloring plastics or imparting other properties to plastics.
  • masterbatch including CNFs, MAPP, and/or PP was produced first and then the ground pellets from masterbatch was redispersed into the PP matrix using extrusion process to produce the composites.
  • the MAPP emulsion treated CNF suspension was dried and then the dried mixture of CNFs and MAPP was compounded with PP to generate the masterbatch of PP+CNF MAPP.
  • the final composite was manufactured using the same extrusion process.
  • the pure PP and blends of PP and 2 wt. % MAPP pellets were also processed using the same extrusion procedures.
  • a thermal compounding process used to produce the masterbatch materials was performed on a C. W. Brabender Prep Mixer® (C. W. Brabender Instruments, INC., Southhackensack, NJ) by controlling the temperature of the mixing bowl which has a capacity of 200 grams.
  • the polymer pellets (PP or PP plus MAPP) were initially melted at 200 °C and then compounded with the corresponding weight of CNFs or treated CNFs in the Brabender for about 8-10 minutes at 200 °C with mixing bowl rotating at the speed of 60 rpm, followed by grinding.
  • the PP pellets, MAPP pellets, CNFs were dried in an oven at 105 °C for 2 h.
  • the ground masterbatch pellets were mixed with PP pellets and then were extruded at 60 rpm through the C. W. Brabender 20 mm Clamshell Segmented Twin Screw Extruder attached to the Intelli-Torque Plastic-Corder drive system (C. W. Brabender
  • the pellets were fed into the first zone of the extruder through the feed hopper at about 70 g/min.
  • the screw configuration of the system was Stand-alone TSE20/40D.
  • the five heating zones were all set up at 200 °C.
  • the composite extrudate was passed through a two-nozzle die with the diameter of each nozzle 2.7 mm.
  • the die temperature was also maintained at 200 °C.
  • the extrudate, in its melt state, was cooled and solidified directly in an air-cooling system while being pulled with a 2200 Series End Drive Conveyor from DORNER MFG. Corp. (Hartland, WI).
  • Particle size distributions of CNFs were determined using a Mastersizer 2000 particle size analyzer (Malvern Instruments, Malvern, UK), for dry samples analysis using the Sirocco 2000 dry dispersion unit and for suspension samples analysis using the Hydro 2000S unit.
  • the operation principle of this equipment is based on the technique of laser diffraction, which takes advantage of the phenomenon that particles scatter light in all directions with an intensity angular pattern that is dependent on particle size. Larger particles will scatter at small angles and smaller particles scatter at wide angles. With the detection of the intensity pattern, the particle size can be determined using Mie theory (Mie 1908).
  • Mie theory Mie theory
  • the melt flow index is defined as the mass of a polymer melt in grams extruded in ten minutes through a standard capillary of a specific diameter and length in a melt floe indexer when a fixed pressure is applied to the melt at a prescribed temperature, as specified by ASTM D1238-10. Melt flow index of all the composite samples were measured using the Dynisco Melt Flow Indexer Model 4004 (Morgantown, PA). The standard die used inside the barrel of Dynisco Melt Flow Indexer had an orifice diameter of 2.095 mm and length of 8 mm. The instrument was first heated to the test temperature of 230 °C and maintained for at least 15 minutes prior to charging the composite samples.
  • a measured quantity of material (ranging from 3-5 g) in pellet form after extrusion was charged to the barrel and packed down.
  • the piston was then inserted into the barrel and the test weight of 2.16 kg was added on top of the piston after a 2-minute "melt" period, commencing the extrusion.
  • the extrudate cut-off time -interval was set up as one minute according to ASTM D 1238 for the composite samples. Cutting of extrudates was completed manually. Extrudates were discarded if there were visible bubbles. Five extrudates were collected for each sample and weighed to the nearest 1 mg. The average value was calculated and then was converted to the standard melt flow rate number with the units of g/10 minute. Tests were considered valid if the difference between the average and maximum and minimum values was not greater than 15% of the average value.
  • the standard percentile readings D (n, 0.1), D (n, 0.5), and D (n, 0.9) of particle sizes derived from the statistics of the distribution are 8.9, 43.4, and 151.6 ⁇ , e. g., 50 % of the CNFs by volume in suspension is smaller than 43.4 ⁇ .
  • Adding MAPP emulsion with solid content (maleated polypropylene) particle sizes from 1.5 to 84.3 ⁇ (MAPP in FIG. 2) in the CNF suspension changed the particle size distribution of the CNFs.
  • a second peak of about 7.7 % by volume with particle sizes from about 266.7 to 843.4 ⁇ was observed on the particle size distribution curve (CNF 2 in FIG.2).
  • Polypropylene part in MAPP molecules form the core with the CNFS parts as the tails contacting with surrounding water.
  • the decreased proportion of particles in the smaller sizes appears to validate this theory.
  • the particle size distributions of dried CNFs (CNF in FIG. 2) characterized using the same technique are shown as black lines in FIG. 2.
  • the particle sizes of dried CNFs ranges from 0.1 to 266.7 ⁇ with the standard percentile readings D (n, 0.1), D (n, 0.5), and D (n, 0.9) of 2.4, 10.0, and 55.4 ⁇ , respectively.
  • the particle sizes of dried CNFs are significantly smaller and the distribution is narrower. Exclusion of larger size of CNFs from suspension was observed in the spray-drying process. A lot of CNFs were deposited on the drying chamber wall. The smallest particle decreased from 0.6 ⁇ in suspension to 0.1 ⁇ in dry form.
  • the drying process may fold the longer soft CNFs in suspension, forming smaller or different shape particles which generate smaller size in the laser diffraction measurement.
  • the CNFs treated with MAPP emulsion (MAPP CNF in FIG. 2) after drying showed similar particle size distribution with pristine CNFs except the greater proportion of relative large particle size ranging from 84.3 to 266.7 ⁇ .
  • the standard percentile readings for D (n, 0.1) and D (n, 0.5) are slightly greater than that of the pristine CNFs with values of 2.7 and 11.1 ⁇ while the value of D (n, 0.9) shift to a greater number of 84.8 ⁇ .
  • the differences of the three readings demonstrate the effect of the MAPP emulsion treatment.
  • the larger particles of the treated CNFs which were possibly caused by grafting of MAPP molecules were eliminated, resulting in the possibility of less content of MAPP on the dried CNFs than the designed value.
  • the SEM micrograms of the dried CNFs are shown in FIG. 3.
  • fibrous materials with different diameters and length are observed: fibrous materials with different diameters and length, ribbon-like (or platelet) materials with different thickness, width, or length, and irregular shape of materials with different degree of agglomeration.
  • the fibrous CNF diameters range from about 0.1 to several ⁇ with the length up to about 500 ⁇ .
  • the ribbon- like materials are generally several ⁇ in width, submicron meters in thickness, and tens of micron meters in length. These two types of CNFs are generally formed during the CNF manufacturing process.
  • melt flow index is a measure of flow inversely related to melt viscosity.
  • melt flow index of PP after the extrusion process is 7.2 g/10 min.
  • MFI of the mixture increased to 9.3 g/10 min, which is the expectation of adding lower viscosity of MAPP pellet.
  • the addition of 6 wt. % of spray-dried CNFs into PP the mixture showed a higher MFI (lower viscosity) compared with Generally, the addition of natural fiber to polymer composites is known to restrict molecular motion in the matrix and cause the lowering of MFI values (see Jam and Behravesh, Flow behavior of HDPE-fme wood particle composites, 2007, J.
  • the small size of CNFs may form significant amount of separate surfaces. Air might be trapped in the space between CNFs and PP, facilitating the motion of polymer molecules and CNFs.
  • the high measurement temperature of 230 °C and the retention melting time (2 minutes) inside of the melt flow indexer barrel may also contribute to the formation of volatile between CNFs and PP because of the decomposition or dehydration of CNFs.
  • separation of PP molecules by CNFs decreased the entanglement density of PP molecules, resulting in higher MFI value. Utilization of MAPP in the PP/CNFs system decreased the MFI value (Table 2). Cross-linking between CNFs and PP may be established, decreasing the amount of separation surfaces.
  • the tensile testing results for all the composites are shown in FIG. 4 and Table 3, including tensile modulus of elasticity (MOE) and tensile strength.
  • MOE tensile modulus of elasticity
  • the statistical analyses on the tensile MOE and tensile strength of the different composites were performed at a 0.05 significance level. The results are shown in Table 3 with brackets.
  • the values with different letters (A, B, C, and D) are significantly different from one another (i.e., "A” is statistically different from "B", “C", and “D”, etc).
  • PP had a tensile MOE and tensile strength of 1.43 GPa and 29.5 MPa, which are the lowest values among all the composites.
  • PP sample Under the tensile load, PP sample responded with an initial elastic deformation, followed quickly by a viscoelastic part, where the stress gradually increased to reach a maximum at a yield point. After the yield point, continued deformation resulted in necking and propagation of neck along the sample length. The stress decreased towards a plateau value with the occurrence of cold drawing until the specimen failed.
  • the tensile MOE of PP was calculated using the elastic behavior during the tensile test while the tensile strength was derived from the yield point. Addition of two weight percentage of MAPP pellets into PP did not change the tensile behavior of PP. The obtained tensile MOE and tensile strength are not significantly different from pure PP (table 3 and FIG. The tensile deformation processes observed in CNFs reinforced PP were different from pure PP. All the samples failed at lower tensile strain compared to pure PP. The tensile strains at the maximum load of all the composites are also decreased. The data measured during the tensile test are shown in Table 2.
  • the tensile MOE (1.96 GPa) of PP reinforced by CNFs treated with MAPP emulsion is about 37 % higher than that of pure PP (1.43 GPa) and composite produced by addition of MAPP pellets into the PP/CNFs system (PP+MAPP+CNF) showed about 36 % higher tensile MOE (1.94 GPa) than PP.
  • the tensile strain at the maximum load decreased from 9.2 % for PP to 6.1 % and 6.7 % for PP+MAPP CNF and PP+MAPP+CNF, respectively.
  • Tensile MOE is related to the ratio between stress and strain at the elastic stage of a tensile test.
  • the tensile MOE of the reinforced composites is generally determined by the elastic properties of their components. With the addition of stiff er CNFs in PP, the composite modulus can be easily improved. On the molecular level, the motion of PP molecules in CNFs reinforced PP composites was restrict by CNFs, resulting in higher stress at the elastic stage of the tensile test compared to the stress in pure PP. It is noteworthy that the addition of MAPP in the composite of pristine CNFs reinforced PP, which was used to increase the interfacial adhesion between CNFs and PP, significantly improved the tensile MOE.
  • the higher tensile MOE could be caused by: (1) the higher content of CNFs in the spray-dried sample of MAPP CNF and/or (2) the different particle size distribution of MAPP treated CNFs and pristine CNFs.
  • MAPP content could be lower than the designed value while the CNFs content could be higher, resulting in the higher weight percentage of CNFs in the final composites.
  • the modulus of reinforced composites consistently increases with increasing content of reinforcement.
  • MAPP pellets in the system of PP/CNFs increased the compatibility between CNFs and PP, facilitating the even dispersion of CNFs in PP.
  • the tensile MOE was improved.
  • the improved tensile MOE could also be associated with the crystalline structure of the composite.
  • PP reinforced by MAPP pellet treated CNFs (32.8 MPa) is about 11 % higher than that of pure PP (29.5 MPa).
  • the reinforcement of MAPP emulsion treated CNFs the tensile strength of PP increased to 31.2 MPa, which is about 6 % higher than that of pure PP (Table 3).
  • the tensile strength of the composite is defined as the yielding stress that the composite can sustain under uniaxial tensile loading.
  • the yielding point is considered to be associated with the onset of significant plastic flow.
  • the yielding behavior is associated with inter-chain sliding, chain segmental motion, and chain reconformation.
  • MOE a GPa) Strength (MPa) MOE (GPa) Strength (MPa) ( kJ/m )
  • the direction at 45 degree to the tensile axis is the principal shear stress direction, i.e., the optimum position for the PP chain slip. Failure of the outer PP layer induced by crack, which was initiated by crazing, was also observed in FIG. 5A.
  • the initial craze formed at the yield point of tensile test propagates through the cross-section with the formed fibrous structures stretching in the tensile axis. Micro-voids are generated because of fragmentation and splitting of the stretched fibrils.
  • coalescence of the micro-voids forms larger size void or crack, resulting in failure on the outside layer of PP shown in FIG. 5A.
  • Fine crazing and tearing bands along the tensile axis can also be observed after the failure of outer layer in FIG. 5A. Additional stress-whitening occurred at the same time as crazing started and also in the necking phase during the tensile test.
  • FIG. 5B The cross-sections of broken samples after the tensile test were also examined using SEM (FIG. 5B).
  • Four different fracture morphologies are observed in FIG. 5B: region 1, crazing-tearing; region 2, brittle fracture with ductile pulling of fibrils/micro fibrils; region 3, fibrillation (disentanglement); and region 4, scission.
  • the morphology in region 1 of FIG. 5B is similar to the fracture morphology formed in FIG. 5A, which is defined as crazing-tearing in the study of Dasari et al. (2003).
  • the higher magnification of crazing-tearing fracture morphology is shown in FIG. 5C.
  • region 2 of FIG. 5B The higher magnification SEM microgram of region 2 in FIG. 5B is shown in FIG. 5D.
  • FIG. 5D The higher magnification SEM microgram of region 2 in FIG. 5B is shown in FIG. 5D.
  • FIG. 5D The higher magnification SEM microgram of region 2 in FIG. 5B is shown in FIG. 5D.
  • the region 2 is the transition phase from crazing-tearing of region 1 to fibrillation occurred in region 3 of FIG. 5B.
  • High density fibrillation of the stretched crazing bands is observed in region 3.
  • FIG. 6 The fracture surface morphologies of CNFs (treated and untreated) reinforced PP are shown in FIG. 6. As shown in FIG. 6, addition of CNFs in PP completely changed the fracture morphologies. Only one type of fracture surface morphology was observed. All the fracture surfaces of the composites become rough compared with pure PP (FIG. 6A). In the composites, PP and CNFs composed a heterogeneous system with different resistance capacity to the applied force. Under the uniaxial tensile load, non-consistent motions between PP and CNFs occurred and cause debonding between PP and CNFs, forming the fracture morphology of fibrillation as shown in FIG. 6B.
  • FIGs. 6C, D, E and F The higher magnification SEM micrograms of CNFs in PP are shown in FIGs. 6C, D, E and F.
  • FIG. 6C shows no connection between CNFs and PP in the sample of pristine CNFs reinforced PP (PP+CNF) while FIGs. 6E and F indicates strong interactions between CNFs and the polymer matrix in the sample of PP+MAPP+CNF.
  • PP+MAPP+CNF a significantly higher tensile strength (32.8 MPa) was obtained for PP+MAPP+CNF compared to PP+CNF (30.4 MPa).
  • PP+MAPP CNF shows no interaction between CNFs and polymer matrix (FIG. 6D), a similar case to pristine CNFs reinforced PP.
  • the tensile strength of PP reinforced by MAPP emulsion treated CNFs is higher than that of pristine CNFs reinforced PP.
  • MAPP emulsion treatment worked but it is not as efficient as MAPP pellet treatment.
  • the MAPP molecules may be buried inside of CNF agglomerates, preventing contact with PP in extrusion process.
  • the possibility of excluding MAPP during the spray-drying process may contribute to the different mechanical properties, too.
  • the different particle size distributions may also offer another explanation.
  • MAPP emulsion treatment on CNFs needs to be optimized.
  • PP reinforced with MAPP emulsion treated CNFs showed lower tensile strain (6.1%) at the maximum load compared to PP reinforced with CNFs (6.4 %) and MAPP pellet treated CNFs (6.7 %).
  • MAPP emulsion treatment on CNFs resulted in a greater proportion of relative large particle size (84.3-266.7 ⁇ ) after spray-drying compared with spray-dried pristine CNFs.
  • the relatively greater proportion of large particle size may cause the lowest tensile strain at the maximum load for PP reinforced by the MAPP emulsion treated CNFs.
  • the Izod impact property with notching for all the composites in this Example were measured according to ASTM D 256-10.
  • the impact resistance data are shown in Table 3 and FIG. 8.
  • the statistical analysis was conducted on the impact resistance at a 0.05 significance level.
  • the impact resistance of pure PP is 3.1 kJ/m 2 .
  • the fracture cross-section was examined using SEM and the micrograms are shown in FIGs. 9 A and B.
  • the low magnification microgram (FIG. 9A) indicates that the fracture initiated at a distance (about 300 ⁇ ) from the notching line (the white arrow in FIG. 9A) and propagated outwards towards the surface of the sample.
  • MAPP CNF Good dispersion of MAPP CNF was also observed. Similar to the sample of pristine CNFs reinforced PP, brittle failure and a big amount of exposed CNFs are observed on the surface. However, close-up examination of fracture surface of PP+MAPP CNF indicated that a proportion of CNFs is bonded with the polymer matrix (FIG. 9F). MAPP emulsion treatment on CNFs built this interfacial adhesion. In general, interfacial adhesion between reinforcements and matrix has a significant effect on composite impact resistance (see Fu et al. 2008). Generally, strong adhesion leads to high impact resistance. In this case, however only a very small amount of interfacial adhesion was built between CNFs and PP and did not increase the impact resistance. The different particle size distributions of MAPP CNFs and CNFs may also partially balance the effect of MAPP treatment.
  • MAPP pellet is maleic anhydride grafted low molecular weight PP with very high melt flow index (115 g/10 minutes at 190 °C with the load of 2.16 kg). Addition of MAPP pellets in PP decreased the MFI of PP from 7.2 to 9.3 g/10 minute.
  • the fracture surface of PP+MAPP was examined using SEM, and the micrograms are shown in FIGs. 10A, C, and E. Similar to pure PP, the fracture initiated at a distance of about 300 ⁇ from the notching line and propagated towards the surface of the sample (FIG. 10A). The low magnification microgram of PP+MAPP (FIG.
  • FIG. 10A also shows that a brittle failure mode similar to pure PP was observed except a number of additional white areas included (white circular area in FIG. 10A).
  • the close- up examination on the white circular area using SEM obtained the microgram of FIGs. IOC and E. Materials with the shape of dendritic crystal in the dimensions of several micron meters are observed.
  • the effect of adding MAPP on the crystallization behavior of PP was previously studied, and it is thought that MAPP functions as a nucleating agent in PP and influence the crystallization of PP (see Seo et al., Study of the crystallization behaviors of polypropylene and maleic anhydride grafted polypropylene, 2000, Polymer, 41 : 2639-2646).
  • the dendritic shape material may represent the crystalline structure change in the mixture of PP and MAPP which possibly leads to the enhancement of the impact resistance of PP.
  • the crystalline structure change by adding MAPP in PP may also explain the enhancement of the flexural MOE and flexural strength of PP+MAPP.
  • composite consisted of PP, MAPP pellets, and CNFs showed a further higher impact resistance (3.8 kJ/m 2 ). It is about 23 % higher than that of pure PP and 27 % higher than pristine CNFs reinforced PP.
  • the cross-section fracture morphologies are shown in FIGs. 10B, D, and F. The fracture morphology in FIG.
  • FIG. 10B showed brittle failure mode with no observable fracture initiation point, indicating there might be no stress concentrating point during the impact test and good dispersion of CNFs. Significantly less numbers of exposed CNFs are observed. No separated surface and hole is observed. The higher magnification SEM micrograms shown in FIGs. 10D and F indicated that a strong interfacial adhesion was established. After the impact test, splitting of the CNFs was even observed (FIG. 10D). Therefore, the impact resistance of PP+MAPP+CNF was significantly increased compared to all the other composites.
  • CNFs cellulose nanofibrils
  • PP polypropylene
  • MAPP maleic anhydride-grafted polypropylene
  • the first method was in situ modification of CNFs in original suspension with MAPP emulsion during the spray-drying process.
  • the second method was performed using MAPP pellets when mixing spray-dried CNFs with PP during the extrusion process.
  • slight differences in particle size distribution were observed for pristine CNFs and MAPP emulsion treated CNFs.
  • Pure PP had the lowest melt flow index while the mixture of PP and MAPP pellets had the highest melt flow index.
  • the melt flow indices of all the CNFs reinforced composites were fond to be located between PP and the mixture of PP and MAPP pellets.
  • the tensile MOE and tensile strength were 1.94 GPa and 32.8 MPa, which represent about 36 % and 11 % improvement compared to the tensile MOE (1.43 GPa) and tensile strength (29.5 MPa) of pure PP.
  • the fiexural MOE of PP+MAPP+CNF (1.63 GPa) was about 21 % higher than that of pure PP.
  • the highest fiexural strength was obtained for pristine CNFs reinforced PP (52.4 MPa) which is not significantly different from that of PP+MAPP+CNF (50.1 MPa).
  • Composite of PP+MAPP+CNF also has the highest impact resistance of 3.8 kJ/m 2 .
  • CNP cellulose nanoparticles
  • the average size of the CNP ranged within few micrometers including a significant amount of nano-dimensioned particles (at least 30%).
  • the CNP was processed using conventional polymer processing methods with impact modified polypropylene (IMPP) as a polymer matrix.
  • IMPP impact modified polypropylene
  • the loading level of CNP in this Example was 6% by weight, which was pre-coated with maleic anhydride grafted polypropylene (PP-g-MA), a coupling agent, by using a master batching process similar to that described above in Example 1.
  • thermoplastic composites increase the stiffness with a critical loading level, such as two digit percentiles, due to the much higher modulus of the fillers/additives as compared to the matrix polymer(s) themselves.
  • One advantage provided by various embodiments include a relatively lowered cost, given the low amounts of filler/additive used, in fact, CNP can be competitive to the carbon nanotubes or even carbon fibers or glass fibers.
  • a second advantage is the use of cellulose, which is an environmentally friendly additive.
  • a master batch was prepared using CNP with PP-g-MA, a coupling agent, in an extrusion process.
  • the master batch was compounded again with IMPP, resulting in 6% wt. of the loading level of CNP and 2% wt. of the PP-g-MA.
  • the mechanical properties are shown at FIG. 11.
  • IMPP-MB impact modified polypropylene processed for master batch
  • IMPP-CNP IMPP filled with CNP only
  • IMPP-g-MAPP IMPP filled with CNP and PP-g-MA.

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Abstract

La présente invention concerne, entre autres, des compositions contenant des nanofibrilles, au moins un copolymère anhydride maléique (MA) et au moins une matrice polymère, et des procédés de préparation de ces compositions. Ces procédés et ces compositions permettent de produire des composites à propriétés étonnamment supérieures présentant une résistance améliorée aux chocs, un module d'élasticité en traction amélioré, une résistance améliorée à la traction, et un module d'élasticité en flexion amélioré par rapport aux composites connus précédemment. Dans certains modes de réalisation, la présente invention concerne des procédés qui comprennent les étapes consistant à produire des nanofibres de cellulose, à associer ces nanofibres de cellulose au copolymère anhydride maléique (MA) afin de former un mélange nanofibrille-copolymère MA destiné à être ajouté à une matrice polymère, et à former un composite par association du mélange nanofibrille-copolymère MA et de la matrice polymère, la quantité de nanofibres de cellulose dans le composite étant comprise entre 3 et 50% en poids du composite.
EP14826568.9A 2013-07-18 2014-07-17 Composites polymère-nanofibrille Active EP3022255B1 (fr)

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US20160369125A1 (en) * 2015-06-16 2016-12-22 Ut Battelle, Llc Thermoset composite having thermoplastic characteristics
KR102574040B1 (ko) * 2015-06-30 2023-09-04 에센티움 메터리얼스, 엘엘씨 셀룰로오스 나노물질을 갖는 합성 개질된 열가소성 고분자 복합체
US10793700B2 (en) * 2015-09-17 2020-10-06 GranBio Intellectual Property Holdings, LLC Compatibilizers for polymer-nanocellulose composites
WO2017057699A1 (fr) * 2015-09-30 2017-04-06 株式会社日本製鋼所 Dispositif de production en continu de cellulose chimiquement modifiée et procédé utilisé dans ce dernier
US10532383B2 (en) * 2015-10-30 2020-01-14 Canon Kabushiki Kaisha Method of producing three-dimensional object and removing liquid to be used in the production method
JP7123901B2 (ja) * 2016-03-31 2022-08-23 ウエスト フレイザー ミルズ リミテッド 木材パルプを含むセルロース複合材料を製造するプロセス
US10767018B2 (en) * 2016-08-26 2020-09-08 Csir Isotactic polypropylene based composite
KR101985710B1 (ko) * 2016-12-02 2019-06-05 한국생산기술연구원 대나무를 포함하는 3d 프린팅용 열가소성 소재
JP2019026658A (ja) * 2017-07-25 2019-02-21 花王株式会社 熱可塑性樹脂組成物の製造方法
CN111566161A (zh) * 2017-11-16 2020-08-21 缅因大学系统董事会 用于3d打印的改进的长丝
US11479657B2 (en) * 2018-05-18 2022-10-25 Paul Albee, SR. System and method for fabricating nanoparticle filler material dispersions and producing improved compounds containing hydrophobic plastic polymers
US20210380787A1 (en) * 2018-10-22 2021-12-09 GranBio Intellectual Property Holdings, LLC Methods for improving nanocellulose dispersion in elastomeric compounds, and compositions containing dispersed nanocellulose in elastomer compounds
EP4047040A4 (fr) * 2019-10-17 2023-01-18 National University Corporation Shizuoka University Procédé de production de complexe de cellulose, procédé de production de composition de résine/complexe de cellulose, complexe de cellulose et composition de résine/complexe de cellulose
CN112092277B (zh) * 2020-08-05 2022-02-25 江苏佳境生态工程技术有限公司 透水塑胶道路面层颗粒制造工艺
CN115716961B (zh) * 2022-11-30 2024-05-14 金发科技股份有限公司 一种聚丙烯组合物及其制备方法

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ES2788658T3 (es) 2020-10-22
EP3022255B1 (fr) 2020-02-12
WO2015009972A1 (fr) 2015-01-22
BR112016000813A2 (pt) 2017-07-25
EP3022255A4 (fr) 2017-04-12
BR112016000813B1 (pt) 2021-08-03
CA2918313A1 (fr) 2015-01-22
US10280294B2 (en) 2019-05-07
CA2918313C (fr) 2021-07-13

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